Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, Singapore 637371.
Chemistry. 2013 Aug 26;19(35):11786-90. doi: 10.1002/chem.201300255. Epub 2013 Jul 12.
The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [LSi:]2 (1; L = PhC(NtBu)2) with one equivalent of N-trimethylsilyl-4-dimethylaminopyridinium triflate [4-NMe2C5H4NSiMe3]OTf and two equivalents of DMAP in THF afforded [LSi(DMAP)]OTf (2). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [L'2(L)Si]OTf (3; L' = LSi:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)3}] and elemental sulfur in THF afforded the silylsilylene [LSiSi(H){(NtBu)2C(H)Ph}] (4) and the base-stabilized silanethionium triflate [LSi(S)DMAP]OTf (5), respectively. Compounds 2, 3, and 5 have been characterized by X-ray crystallography.
描述了一种由酰胺基配体和 4-二甲氨基吡啶（DMAP）稳定的硅鎓阳离子的合成和反应性。酰胺基硅（I）二聚体[LSi:]2（1；L = PhC（NtBu）2）与等摩尔的 N-三甲基甲硅烷基-4-二甲氨基吡啶三氟甲磺酸酯[4-NMe2C5H4NSiMe3]OTf 和两当量的 DMAP 在 THF 中反应得到[LSi（DMAP）]OTf（2）。2 的两性特征从其反应性得到证明。在 THF 中用 1 处理 2 得到双硅亚基硅鎓三氟甲磺酸酯[L'2（L）Si]OTf（3；L'=LSi：），同时 DMAP 被取代。2 与[K{HB（iBu）3}]和元素硫在 THF 中的反应分别得到硅硅亚基[LSiSi（H）{（NtBu）2C（H）Ph}]（4）和碱稳定的硅硫翁三氟甲磺酸酯[LSi（S）DMAP]OTf（5）。化合物 2、3 和 5 已通过 X 射线晶体学进行了表征。
